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(11) | EP 1 323 808 B1 |
| (12) | EUROPEAN PATENT SPECIFICATION |
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Organic Electroluminescent Device Organische elektrolumineszente Vorrichtung Dispositif organique électroluminescent |
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| Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). |
BACKGROUND OF THE INVENTION
Field of the Invention
[0001] The present invention relates generally to an organic electroluminescent device in which a luminescent layer and a carrier transporting layer using an organic material are formed between a hole injection electrode and an electron injection electrode, and more particularly, to an organic electroluminescent device capable of stably emitting light having uniform and sufficient luminance because an organic material used for a luminescent layer and a carrier transporting layer is hardly crystallized.
Description of the Prior Art
[0002] In recent years, the needs of plane display devices the consumed power and the volume of which are smaller than those of a CRT which has been conventionally generally employed have been increased as information equipments are diversified, for example. An electroluminescent device (hereinafter referred to as an EL device) has been paid attention to as one of the plane display devices.
[0003] The EL device is roughly divided into an inorganic EL device and an organic EL device depending on a used material.
[0004] The inorganic. EL device is so adapted that a high electric field is generally exerted on a luminescent portion, and electrons are accelerated within the high electric field to collide with a luminescence center; whereby the luminescence center is excited to emit light.
[0005] On the other hand, the organic EL device is so adapted that electrons and holes are respectively injected into a luminescent portion from an electron injection electrode and a hole injection electrode, the electrons and the holes thus injected are recombined with each other in a luminescence center to bring an organic molecule into its excited state, and the organic molecule emits fluorescence when it is returned from the excited state to its ground state.
[0006] In the inorganic EL device, a high voltage of 100 to 200 V is required as its driving voltage because a high electric field is exerted as described above. On the other hand, the organic EL device can be driven at a low voltage of approximately 5 to 20 V.
[0007] In the organic EL device, a light emitting device emitting light in a suitable color can be obtained by selecting a fluorescent material which is a luminescent material. It is expected that the organic EL device can be also utilized as a multi-color or full-color display device or the like. Further, it is also considered that the organic EL device is utilized as a backlight of a liquid crystal display device or the like because it can surface-emit light at a low voltage.
[0008] In recent years, various studies have been undertaken on such an organic EL device. Developed examples of the organic EL device include ones having a three-layer structure which is referred to as a DH structure in which a hole transporting layer, a luminescent layer and an electron transporting layer are laminated between a hole injection electrode and an electron injection electrode, a two-layer structure which is referred to as an SH-A structure in which a hole transporting layer and a luminescent layer abundant in electron transporting characteristics are laminated between a hole injection electrode and an electron injection electrode, and a two-layer structure which is referred to as an SH-B structure in which a luminescent layer abundant in hole transporting characteristics and an electron transporting layer are laminated between a hole injection electrode and an electron injection electrode.
[0009] In the organic EL device, a uniform layer is formed by vacuum evaporation or the like in forming the luminescent layer and the carrier transporting layer. The stability of an organic material in the luminescent layer and the carrier transporting layer is not sufficient, and the organic material is gradually crystallized so that its crystals are deposited on the luminescent layer and the carrier transporting layer with an elapse of time. As a result, a short circuit, for example, occurs in the organic EL device, whereby it is impossible to obtain light having uniform and sufficient luminance in the entire organic EL device.
[0010] When the organic EL device is utilized as a backlight of a liquid crystal display device or the like, white light emission is required in that the display is easy to see, for example. However, the organic EL device conventionally utilized generally emits light in various colors.
[0011] In recent years, in order to obtain white light emission by the organic EL device, a method of doping three types of luminescent materials emitting light in the three primary colors, red (R), green (G) and blue (B) into a host material and uniformly emitting light in red, light in green and light in blue to obtain white light emission [J. Kido, K. Hongawa, K. Okuyama, and K. Nagai ; Appl. Phys. Lett. 64 (1994) 815], and a method of laminating three types of luminescent layers using three types of luminescent materials emitting light in the three primary colors, red (R), green (G) and blue (B) and uniformly light in red, light in green and light in blue from the respective luminescent layers to obtain white light emission [Sato, Extended Abstracts (The 55th Autumn Meeting, 19p-H-7, 1994) The Japan Society of Applied Physics] have been proposed.
[0012] In either one of the above-mentioned methods, however, light in red, light in green and light in blue must be uniformly emitted. In order to make such an adjustment that the emission intensities are uniform, the amount of each of the luminescent materials doped into the host material, the thickness of each of luminescent layers, and the like must be strictly controlled. Therefore, the fabrication of the organic EL device is very difficult, whereby it is very difficult to obtain constant white light emission. For example, emitted white light is tinged with a certain type of color.
[0013] When the above-mentioned organic EL device is utilized as a multi-color or full-color display device, tris (8-hydroxyquinolinate) aluminum (hereinafter abbreviated as Alq3) indicated by the following chemical formula 1, for example, has been conventionally generally utilized as an organic luminescent material in obtaining light emission in green which is one of the three primary colors R, G and B.
[0014] However, the melting point of Alq3 is as high as 412°C, and Alq3 does not easily sublime. When a luminescent layer is formed by vacuum evaporation or the like, as described above, Alq3 must be heated to approximately 300°C by resistive heating or the like, whereby a large amount of energy is required to form the luminescent layer. Therefore, the cost of the organic EL device is high, and the productivity thereof is reduced. Since the temperature of Alq3 is increased in forming the luminescent layer, as described above, an organic material in a carrier transporting layer formed prior to the luminescent layer is degraded.
[0015] EP-A-0 652 273 discloses an electroluminescent device with a luminescent layer containing a 2-(O-hydroxyphenyl)-benzoxazole or -benzothiazole zinc complex.
[0016] JP-A-06 336586 discloses electroluminescent chelate complexes in which the central metal can be selected from the group II of the periodic table.
[0017] EP-A-0 710 655 (prior art under Art. 54(3) EPC) discloses green-emitting benzotriazole metallic complexes for use in light emitting devices.
SUMMARY OF THE INVENTION
[0018] An object of the present invention which is defined in the claims is to provide, in an organic EL device in which a luminescent layer and a carrier transporting layer using an organic material are formed between a hole injection electrode and an electron injection electrode, an organic EL device capable of emitting light having uniform and sufficient luminance for a long time period by preventing an organic material used for a luminescent layer and a carrier transporting layer from being gradually crystallized with an elapse of time to deposit crystals on the luminescent layer and the carrier transporting layer.
[0019] In an organic EL device according to the present invention, in which at least a carrier transporting layer and a luminescent layer using an organic material are laminated between a hole injection electrode and an electron injection electrode, a chelate compound, indicated by the following chemical formula 2, having as a ligand a heterocyclic compound is contained in at least one of the carrier transporting layer and the luminescent layer.
[0020] In the foregoing chemical formula 2, X and Z are any elements selected from C, S, Se, Te, N and P, Y is any one element selecting from C, N and P, (A1) is a aromatic radical or a heterocyclic radical in which a hydroxyl group is bound to the Y in an ortho position, and (A2) is a radical which is bound to carbon to which the X is bound and carbon to which the Z is bound to constitute an aromatic compound or a heterocyclic compound.
[0021] As a central metal in the chelate compound indicated by the foregoing chemical formula 2, a metal in Group II of a periodic table and preferably, zinc or beryllium is used.
[0022] When the chelate compound, indicated by the foregoing chemical formula 2, having as a ligand a heterocyclic compound is used for the carrier transporting layer and the luminescent layer as in the organic EL device, the chelate compound is generally difficult to crystallize. Therefore, there is no possibility that crystals are gradually deposited in the luminescent layer and the carrier transporting layer so that a short circuit, for example, occurs as in the conventional organic EL device, whereby it is possible to stably emit light having uniform and sufficient luminance over a long time period.
[0023] As such an organic luminescent material, it is preferable to use a chelate compound which is included in a chelate compound, indicated by the chemical formula 2, having as a ligand a heterocyclic compound and has as a ligand 2 - (2 - hydroxyphenyl) benzothiazole indicated by the following chemical formula 3 or its derivative. R1 and R2 in the following chemical formula 3 may be groups which are bound to a benzene ring to form a polycyclic aromatic compound in addition of substituting groups. It is preferable to use zinc or beryllium as a central metal in the chelate compound.
[0024] In another organic EL device according to the present invention, in providing at least a luminescent layer containing an organic luminescent material between a hole injection electrode and an electron injection electrode, 2 - (2 - hydroxyphenyl) benzothiazole indicated by the foregoing chemical formula 3 or its derivative is used as the organic luminescent material.
[0025] When 2 - (2 - hydroxyphenyl) benzothiazole or its derivative is used as the organic luminescent material in the luminescent layer as in the organic EL device, the melting point thereof is generally lower than that of the Alq3. For example, the melting point of 2 - (2
- hydroxyphenyl) benzothiazole is as low as 129°C, and that is, it may be heated to approximately 100°C, whereby energy required to form the luminescent layer may be small. Therefore, the fabrication cost of the organic EL device is reduced, and the productivity thereof is improved. Further, another organic material used for the carrier transporting layer or the like is hardly degraded by heating in forming the luminescent layer.
[0026] The foregoing and other objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description of the present invention when taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0027]
Fig. 1 is a schematic illustration showing an organic EL device according to an embodiment of the present invention, which has an SH-A structure in which a hole transporting layer and a luminescent layer are laminated between a hole injection electrode and an electron injection electrode;
Fig. 2 is a schematic illustration showing an organic EL device according to an embodiment of the present invention, which has an SH-B structure in which a luminescent layer and an electron transporting layer are laminated between a hole injection electrode and an electron injection electrode; and
Fig. 2 is a schematic illustration showing an organic EL device according to an embodiment of the present invention, which has an SH-B structure in which a luminescent layer and an electron transporting layer are laminated between a hole injection electrode and an electron injection electrode; and
Fig. 3 is a schematic illustration showing an organic EL device according to an embodiment of the present invention, which has a DH structure in which a hole transporting layer, a luminescent layer, and an electron transporting layer are laminated between a hole injection electrode and an electron injection electrode.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0028] Description is now made of preferred embodiments of the organic EL device in the present invention.
[0029] The organic EL device may have any one of an SH-A structure in which a hole transporting layer 3 and a luminescent layer 4 are laminated between a hole injection electrode 2 and an electron injection electrode 6, as shown in Fig. 1, an SH-B structure in which a luminescent layer 4 and an electron transporting layer 5 are laminated between a hole injection electrode 2 and an electron injection electrode 6, as shown in Fig 2 , and a DH structure in which a hole transporting layer 3, a luminescent layer 4, and an electron transporting layer 5 are laminated between a hole injection electrode 2 and an electron injection electrode 6, as shown in Fig. 3.
[0030] Furthermore, in the above-mentioned organic EL device, a material having a large work function such as gold or an indium tin oxide (hereinafter referred to as ITO) is used for the hole injection electrode 2, while an electrode material having a small work function such as magnesium is used for the electron injection electrode 6. In order to take out light emitted in the luminescent layer 4, at least one of the electrodes must be made transparent. Generally, transparent ITO having a large work function is used for the hole injection electrode 2.
[0031] Furthermore, in the above-mentioned organic EL device, a chelate compound having a structure indicated by the following chemical formula 4 exists as the chelate compound, indicated by the foregoing chemical formula 2, having as a ligand a heterocyclic compound which is contained in at least one of the carrier transporting layer and the luminescent layer.
[0032] In the foregoing chemical formulas 2 and 4, as (A1) which is an aromatic radical or a heterocyclic radical in which a hydroxyl group is bound to Y in an ortho position, a radical of a heterocyclic compound such as pyrimidine, triazine, phenazine, or carbazole in which a hydroxl group is bound to Y in an ortho position is used in addition to radicals indicated by the following chemical formulas 5 to 21.
[0033] In the foregoing chemical formulas 2 and 4, as (A2) which is bound to carbon to which X is bound and carbon to which Z is bound to constitute an aromatic compound or a heterocyclic compound, a radical which is bound to carbon to which X is bound and carbon to which Z is bound to constitute a heterocyclic compound such as pyrimidine, triazine, phenazine, or carbazole is used in addition to radicals indicated the following chemical formulas 22 to 34.
[0034] Furthermore, a substituting group may be bound to the above-mentioned (A1) and (A2). The following are examples of the substituting group bound thereto:
- (CnH2n+1), - N(CnH2n+1)2, - F, - Cl, - Br, - I, - O(CnH2n+1), - COO(CnH2n+1), - NO2, - CN, and a phenyl group. Each n in the above-mentioned substituting groups is 0 to 10.
[0035] The organic EL device according to the present invention will be described by taking more specific examples.
(Example 1)
[0036] In an organic EL device in this example 1, a chelate compound indicated by the following chemical formula 36 which is constructed by coordinating two NBTZ indicated by the following chemical formula 35 in zinc (hereinafter referred to as ZnNBTZ) was used as a luminescent material used for a luminescent layer 4.
[0037] In synthesizing the above-mentioned ZnNBTZ, 0.8 g (2.88 mmol) of the above-mentioned NBTZ and 40 ml of methanol which is a solvent were put in a 200 ml eggplant type flask, and 0.32 g (1.44 mmol) of 2 hydrate of zinc acetate was added thereto, after which a cooling pipe was mounted on the flask, to reflux an obtained mixture for six hours. An obtained deposit was filtered and dried, and the filtered and dried deposit was then purified by a sublimating and purifying apparatus using a train sublimation method [H. J. Wagner, R. 0. Loutfy, and C. K. Hsiao ; J. Mater. Sci. Vol. 17, P2781 (1982)], to obtain the ZnNBTZ. The luminescent peak wavelength of the ZnNBTZ was 594 nm, and the half-width of its emission spectrum was 114 nm.
[0038] In this example 1, a transparent hole injection electrode 2 composed of ITO and having a thickness of 2000 Å was formed on a glass substrate 1, and a hole transporting layer 3 composed of N, N' - diphenyl - N, N' - bis (3 - methylphenyl) - 1, 1' - biphenyl - 4, 4' - diamine (hereinafter referred to as TPD) indicated by the following chemical formula 37 and having a thickness of 500 Å, a luminescent layer 4 composed of the ZnNBTZ synthesized in the above-mentioned manner and having a thickness of 500 Å, and an electron injection electrode 6 composed of a magnesium-indium alloy and having a thickness of 2000 Å were successively formed on the hole injection electrode 2, as shown in Fig. 1, to obtain an organic EL device having an SH-A structure.
[0039] A method of fabricating the organic EL device in this example will be specifically described. A glass substrate 1 on which a hole injection electrode 2 composed of ITO is formed was first cleaned by a neutral detergent, and was then ultrasonically cleaned, respectively, in acetone for twenty minutes and in ethanol for twenty minutes. The glass substrate 1 was further put in boiled ethanol for approximately one minute and was taken out, after which the glass substrate 1 was immediately dried by ventilation.
[0040] The above-mentioned TPD was then vacuum evaporated on the hole injection electrode 2 formed on the glass substrate 1, to form a hole transporting layer 3, after which the above-mentioned ZnNBTZ was vacuum evaporated on the hole transporting layer 3, to form a luminescent layer 4. A magnesium-indium alloy was further vacuum evaporated on the luminescent layer 4, to form an electron injection electrode 6. The vacuum evaporation was performed without controlling the substrate temperature at a degree of vacuum of 1 x 10-6 Torr.
[0041] When a positive voltage and a negative voltage were respectively applied to the hole injection electrode 2 and the electron injection electrode 6 in the organic EL device in this example, high-luminance orange light having the maximum luminance of 1800 cd/m2 and having a luminescent peak wavelength of 592 nm was emitted by the ZnNBTZ at a voltage of 16 V.
1. An organic electroluminescent device in which at least a carrier transporting layer
and a luminescent layer using an organic material are laminated between a hole injection
electrode and an electron injection electrode, wherein
a chelate compound, indicated by the following chemical formula, having as a ligand a heterocyclic group is contained in at least one of said carrier transporting layer and said luminescent layer:
wherein, X and Z are any elements selected from C, S, Se, Te, N and P,
Y is any one element selected from C, N and P,
A1 is a condensed polycyclic hydrocarbon radical selected from the group consisting of
A2 is a radical which is bound to the carbon to which said X is bound and the carbon to which said Z is bound to constitute an aromatic compound or a heterocyclic compound,
and the central metal ion M is a metal ion in Group II of the periodic table.
a chelate compound, indicated by the following chemical formula, having as a ligand a heterocyclic group is contained in at least one of said carrier transporting layer and said luminescent layer:
wherein, X and Z are any elements selected from C, S, Se, Te, N and P,
Y is any one element selected from C, N and P,
A1 is a condensed polycyclic hydrocarbon radical selected from the group consisting of
A2 is a radical which is bound to the carbon to which said X is bound and the carbon to which said Z is bound to constitute an aromatic compound or a heterocyclic compound,
and the central metal ion M is a metal ion in Group II of the periodic table.
2. The organic electroluminescent device according to claims 1, wherein the central metal
ion M is zinc or beryllium.
1. Organisches Elektrolumineszenzbauelement, bei dem mindestens eine Trägertransportschicht
und eine Lumineszenzschicht unter Verwendung eines organischen Materials zwischen
einer Lochinjektionselektrode und einer Elektroneninjektionselektrode laminiert sind,
wobei eine durch die folgende chemische Formel angegebene Chelatverbindung mit einer
heterocyclischen Gruppe als Liganden in der Trägertransportschicht und/oder der Lumineszenzschicht
enthalten ist:
wobei X und Z beliebige Elemente sind ausgewählt aus C, S, Se, Te, N und P, Y ein beliebiges Element ist ausgewählt aus C, N und P, A1 ein kondensiertes polycyclisches Kohlenwasserstoffradikal ist ausgewählt aus der Gruppe bestehend aus
A2 ein Radikal ist, das an den Kohlenstoff gebunden ist, an den X gebunden ist, und der Kohlenstoff, an den Z gebunden ist, um eine aromatische Verbindung oder eine heterocyclische Verbindung zu bilden, und das zentrale Metallion M ein Metallion in der Gruppe II des Periodensystems ist.
wobei X und Z beliebige Elemente sind ausgewählt aus C, S, Se, Te, N und P, Y ein beliebiges Element ist ausgewählt aus C, N und P, A1 ein kondensiertes polycyclisches Kohlenwasserstoffradikal ist ausgewählt aus der Gruppe bestehend aus
A2 ein Radikal ist, das an den Kohlenstoff gebunden ist, an den X gebunden ist, und der Kohlenstoff, an den Z gebunden ist, um eine aromatische Verbindung oder eine heterocyclische Verbindung zu bilden, und das zentrale Metallion M ein Metallion in der Gruppe II des Periodensystems ist.
2. Organisches Elektrolumineszenzbauelement nach Anspruch 1, wobei das zentrale Metallion
M Zink oder Beryllium ist.
1. Dispositif électroluminescent organique dans lequel au moins une couche de transport
de support et une couche luminescente utilisant un matériau organique sont stratifiées
entre une électrode d'injection de trous et une électrode d'injection d'électrons,
dans lequel
un composé chélate, indiqué par la formule chimique suivante, ayant, en tant que ligand un groupe hétérocyclique, est contenu dans au moins l'une de ladite couche de transport de support et ladite couche luminescente :
dans laquelle X et Z sont des éléments quelconques choisis parmi C, S, Se, Te, N et P,
Y est un élément quelconque choisi parmi C, N et P,
A1 est un radical hydrocarboné polycyclique condensé choisi dans le groupe constitué par
A2 est un radical qui est lié au carbone auquel est lié ledit X et au carbone auquel est lié ledit Z pour constituer un composé aromatique ou un composé hétérocyclique,
et l'ion métallique central M est un ion métallique du Groupe II du Tableau Périodique.
un composé chélate, indiqué par la formule chimique suivante, ayant, en tant que ligand un groupe hétérocyclique, est contenu dans au moins l'une de ladite couche de transport de support et ladite couche luminescente :
dans laquelle X et Z sont des éléments quelconques choisis parmi C, S, Se, Te, N et P,
Y est un élément quelconque choisi parmi C, N et P,
A1 est un radical hydrocarboné polycyclique condensé choisi dans le groupe constitué par
A2 est un radical qui est lié au carbone auquel est lié ledit X et au carbone auquel est lié ledit Z pour constituer un composé aromatique ou un composé hétérocyclique,
et l'ion métallique central M est un ion métallique du Groupe II du Tableau Périodique.
2. Dispositif électroluminescent organique selon la revendication 1, dans lequel l'ion
métallique central M est le zinc ou le béryllium.